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A theoretical study of large planar [N]phenylenes
Jerome M Schulman1, Raymond L Disch
1Department of Chemistry and Biochemistry of Queens College, and The Graduate Center, The City University of New York, Flushing, New York 11367, USA.
This study explores [N]phenylenes, revealing linear correlations between double-bond localization and aromaticity indicators like NICS(1) values. These findings help predict molecular stability and reactivity in complex ring systems.
Area of Science:
- Computational chemistry
- Organic chemistry
- Aromaticity studies
Background:
- [N]phenylenes are complex aromatic systems.
- Understanding their electronic properties is crucial for predicting stability and reactivity.
Purpose of the Study:
- To investigate the relationship between double-bond localization and aromaticity in 14 [N]phenylenes.
- To correlate molecular properties like energy and heat of formation with structural parameters.
Main Methods:
- Ab initio computational studies were performed on 14 [N]phenylenes with 12-membered rings.
- Analysis included geometries, energies, heats of formation, NICS(1) values, and proton chemical shifts.
- Quantification of double-bond localization (DeltaR) for 58 unique six-membered rings.
Main Results:
- A linear relationship was found between double-bond localization (DeltaR) and NICS(1) values/proton resonances for angular, branched, and terminal rings.
- These parameters are influenced by the number and type of neighboring rings.
- The total molecular bond localization (DeltaRtot) correlates linearly with ab initio energy and heat of formation.
Conclusions:
- Reactions conserving ring types are thermoneutral.
- Net changes in DeltaRtot and DeltaNICS(1) are near zero for such reactions, indicating predictable stability.
- The study provides a quantitative link between structure, aromaticity, and thermodynamic stability in [N]phenylenes.
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